Interference of Humic Substances in the Spectrophotometric Determination of Bromate by Phenothiazines in Natural Waters

Abstract

The spectrophotometric method of bromate (BrO₃ ^?) determination by phenothiazines was applied to natural water samples and the interferences due to the presence of inorganic and humic substances were investigated. Common ions present in natural waters did not interfere and only the less abundant NO₂ ^? and Fe²⁺ exhibited strong interferences. Interferences of the two latter ions, if they existed, could be controlled and the method proved to be accurate and with a low detection limit. However, it was found that the presence of soluble humic substances resulted in positive interference, rendering the method unsuitable for bromate determination in natural waters and restricted its use in pure bromate solutions. This interference can be attributed to the electron acceptor groups invariably existing in the humic molecules. Since humic substances can remain in the water even after its ozonation, they will also contribute to a positive interference in bromate determination in potable waters.     

NMR and theoretical investigations on the structures and dynamics of octahedral bis(chelate)dichloro V(III) compounds isolated by an unusual reduction of non-oxo V(IV) species

Reaction of the non-oxo V(IV) species [V(IV)Cl(2)(L(OO))(2)] [L(OO) = acetylacetonate (acac(-)) or benzoylacetonate (bzac(-))] with a chelate nitrogen-donor ligand L(NN) in acetonitrile leads to the reduction of V(IV) to V(III) and the formation of the mononuclear V(III) compounds of the general formula [V(III)Cl(2)(L(OO))(L(NN))] (L(OO) and L(NN) are acac(-) and bipy for 1; acac- and 5,5'-me(2)bipy for 2; acac(-) and 4,4'-tb(2)bipy for 3; acac(-) and phen for 4; bzac(-) and bipy for 5; bzac(-) and phen for 6). The reduction of the V(IV) complexes was monitored by GC-MS and (1)H NMR spectroscopy. Both one- and two-dimensional (2D COSY and 2D EXSY) (1)H NMR techniques were used to assign the observed (1)H NMR resonances of 1-6 in CD(2)Cl(2) or CDCl(3) solution. It appeared that in solution these V(III) complexes form two isomers which are in equilibrium: cis-[V(III)Cl(2)(L(OO))(L(NN))] <==> trans-[V(III)Cl(2)(L(OO))(L(NN))]. 2D EXSY cross-peaks were clearly observed between bipy- and acac-hydrogen atoms of the two geometrical isomers of 1-3 as well as between bipy and acac(-) protons of the cis isomer, indicating a dynamic process that corresponds to cis-trans isomerization and a cis-cis racemization. The thermodynamic and kinetic parameters of the equilibrium between these two isomers were calculated for compounds 1 and 2 by using variable temperature (VT) NMR data. Both cis-trans isomerization and cis-cis racemization processes probably proceed with an intramolecular twist mechanism involving a trigonal prismatic transition state. Density functional calculations (DFT) also indicated such a rearrangement mechanism.     

Bismuth modified Pd/C as catalysts for hydrogen related reactions

The electrocatalytic activity of bimetallic BiPd catalysts supported on Sibunit carbon towards hydrogen oxidation/evolution reactions (HOR/HER) was studied in a gas diffusion electrode (GDE) setup. Catalysts were synthesized by deposition of Pd on the carbon support, followed by impregnation of Pd/C precursor with Bi(NO₃)₃ solution and reduction in hydrogen. Transmission electron microscopy and local EDX elemental analysis revealed that BiPd/C catalysts contain bimetallic particles with narrow size distribution with maxima at 3.2–4.1 nm. X-ray diffraction evidenced that bimetallic particles are constituted by Pd–Bi solid solution. It was shown that modification of Pd/C by bismuth increases the specific activity of palladium towards HOR/HER by a factor of 3.     

Stability analysis of phase fitted variational integrators

In the present work, we discuss the benefits, limitations and restrictions for the high order phase fitted variational integrators, derived specifically for the numerical integration of systems with oscillatory solutions. To do that, we study linear stability properties of these methods using the eigenvalues of the amplification matrix. The obtained stability region verifies their good behavior, when used for the numerical solution of highly oscillatory problems. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Finite element modelling of surface waves in a channel

A variational formulation of the vertically-integrated differential equations for free surface wave motion is presented. A finite element model is derived for solving this nonlinear system of hydrodynamic equations. The time integration scheme employed is discussed and the results obtained demonstrate its good stability and accuracy.Several applications of the model are considered: the first problem is an open channel of uniform depth and the second an open channel of linearly varying depth. The ‘inflow’ boundary condition is prescribed in terms of the velocity which represents a wavemaker and/or a flow source, while the ‘outflow’ boundary condition is specified in terms of the water elevation. The outflow condition is adjusted for two cases, a reflecting boundary (finite channel) and a non-reflecting boundary (open-ended channel). The latter boundary condition is examined in some detail and the results obtained show that the numerical model can produce the non-reflecting boundary that is similar to the analytical radiation condition for waves. Computational results for a third problem, involving wave reflection from a submerged cylinder, are also presented and compared with both experimental data and analytical predictions.The simplicity and the performance of the computational model suggest that free surface waves can be simulated without excessively complicated numerical schemes. The ability of the model to simulate outflow boundary conditions properly is of special importance since these conditions present serious problems for many numerical algorithms.     

Size-dependent electrocatalytic activity of gold nanoparticles on HOPG and highly boron-doped diamond surfaces

Gold nanoparticles were prepared by electrochemical deposition on highly oriented pyrolytic graphite (HOPG) and boron-doped, epitaxial 100-oriented diamond layers. Using a potentiostatic double pulse technique, the average particle size was varied in the range from 5 nm to 30 nm in the case of HOPG as a support and between < 1 nm and 15 nm on diamond surfaces, while keeping the particle density constant. The distribution of particle sizes was very narrow, with standard deviations of around 20% on HOPG and around 30% on diamond. The electrocatalytic activity towards hydrogen evolution and oxygen reduction of these carbon supported gold nanoparticles in dependence of the particle sizes was investigated using cyclic voltammetry. For oxygen reduction the current density normalized to the gold surface (specific current density) increased for decreasing particle size. In contrast, the specific current density of hydrogen evolution showed no dependence on particle size. For both reactions, no effect of the different carbon supports on electrocatalytic activity was observed.     

On frequency estimations in phase fitted variational integrators for the general N-body problem

In the present work, the advantages of high order variational integrator methods are combined with phase lag properties for the numerical integration of the general N-body problem. Expressing the action integral at any intermediate points along the curve segment using a discrete Lagrangian that depends only on the end points of the interval, high order integrators can be obtained by defining the discrete Lagrangian in any time segment as a weighted sum on intermediate points, whose expressions for positions and velocities use Galerkin interpolation techniques. When oscillatory behavior is taken into account, the methods derived use trigonometric interpolation functions that depend on a frequency, which needs to be estimated. For that, using phase lag analysis, a new way to derive methods has been developed, that uses frequency estimation for each body at every time step. Results on special cases of the N-body problem show more stable orbits and less energy error when compared with the linear interpolation scheme. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mechanism for CuPt-type ordering in mixed III–V epitaxial layers

A model is proposed to rationalize the occurence of CuPt-type ordering in mixed III–V epitaxial layers grown on (001) substrates. It is invoked that 2× surface reconstruction occuring on group V terminated (001) surfaces produces dilated and compressed regions in sub-surface layers. The presence of these regions biases the occupation of certain sites during the growth of a layer consisting of atoms differing in their tetrahedral radii. By assuming that the reconstruction always occurs at the growing surface, it is possible to explain the evolution of CuPt-type ordering in epitaxial layers. Also, based on the model, experimental observations pertaining to the influence of growth conditions, surface misorientation and steps on ordering can be rationalized.